EP2760071B1 - Fuel electrode doubling as support of solid oxide fuel cell and method of producing same - Google Patents

Fuel electrode doubling as support of solid oxide fuel cell and method of producing same Download PDF

Info

Publication number
EP2760071B1
EP2760071B1 EP14150898.6A EP14150898A EP2760071B1 EP 2760071 B1 EP2760071 B1 EP 2760071B1 EP 14150898 A EP14150898 A EP 14150898A EP 2760071 B1 EP2760071 B1 EP 2760071B1
Authority
EP
European Patent Office
Prior art keywords
particles
electrode
oxide
fuel
fuel electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP14150898.6A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2760071A1 (en
Inventor
Takashi Okamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Riken Corp
Original Assignee
Riken Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Riken Corp filed Critical Riken Corp
Publication of EP2760071A1 publication Critical patent/EP2760071A1/en
Application granted granted Critical
Publication of EP2760071B1 publication Critical patent/EP2760071B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H01M4/8621—Porous electrodes containing only metallic or ceramic material, e.g. made by sintering or sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8807—Gas diffusion layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8846—Impregnation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/1213—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the electrode/electrolyte combination or the supporting material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
    • H01M2004/8684—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a fuel electrode that doubles as a support of a solid oxide fuel cell and also to a method of producing the same. Also, the present invention relates to a fuel-electrode-supported solid oxide fuel cell that includes the fuel electrode and a method of producing the same.
  • a solid oxide fuel cell (hereinafter, referred to as SOFC) that generates power by supplying a combustible gas such as hydrogen and an oxidizing gas containing oxygen to a fuel cell configured by separating a fuel electrode and an air electrode with a solid oxide electrolyte has been known. Since the SOFC operates at high temperature and thus has high power generation efficiency as well as being capable of generating power also from a fuel gas other than pure hydrogen, the SOFC is expected as a next generation fuel cell.
  • SOFC solid oxide fuel cell
  • the SOFC is primarily categorized into an electrolyte-supported cell having a thick electrolyte and a fuel-electrode-supported cell having a thick fuel electrode.
  • the electrolyte causes significant internal resistance during power generation
  • the fuel-electrode-supported cell that may have a thin electrolyte has been increasingly used for the purpose of improving a battery performance.
  • JP 10-21932 A (PLT 1) describes a fuel electrode formed of a porous body having a ceramic particle framework. Metal particles, on or in which fine ceramic particles are precipitated, are dispersed inside of holes of the porous body (claim 2).
  • this fuel electrode may be obtained in the following order. First, ceramic powder of YSZ or the like with an average particle diameter of approximately 3 ⁇ m is applied on one surface of a solid electrolyte disc having the air electrode formed on one side thereof and then sintered at approximately 1400 °C, so as to form the porous body having the ceramic particle framework. Thereafter, organic metal compound solution containing at least one metal element of Ni, Co, Fe and Ru, and Zr and/or Ce is poured into the holes of the porous body and thermally decomposed.
  • nickel-zirconia cermet obtained by mixing nickel oxide with an average particle diameter of approximately 1 ⁇ m (NiO, note that it turns Ni metal during operation of the fuel cell) and zirconia (ZrO 2 ) fine particles with an average particle diameter of approximately 0.5 ⁇ m has been known.
  • JP 2009-224346 A (PLT 2) describes a fuel electrode material that consists of a mixture of zirconia coarse particles, zirconia fine particles and nickel or nickel oxide particles, where diameters of these particles satisfy the following relationship: zirconia coarse particles>nickel or nickel oxide particles>zirconia fine particles, and weights of the zirconia coarse particles, the nickel or nickel oxide particles and the zirconia fine particles satisfy the following ratio: 7-4:3-6:1.
  • this fuel electrode material may be obtain by, for example, first mixing YSZ coarse particles and NiO particles for 48 to 60 hours and then adding YSZ fine particles to the mixture, followed by further mixing for about 48 hours.
  • the fuel electrode is in a reducing atmosphere during operation of the SOFC, as hydrogen is supplied to the fuel electrode.
  • the air reaches the fuel electrode and the fuel electrode enters in an oxidizing atmosphere. Therefore, in the course of use repeating operation of SOFC and stop operation, the fuel electrode is exposed alternately to the reducing atmosphere/oxidazing atmosphere.
  • electrode particles Ni of the fuel electrode are oxidized to NiO and a volume of the electrode particles expand. Such irreversible expansion of the electrode particles leads to deterioration of conductivity and strength of the fuel electrode, causing impaired battery characteristics and reduced life of the SOFC. Further, gradual aggregation of the Ni particles in the course of repetition of the reducing atmosphere/oxidizing atmosphere has been also a cause of deterioration of the battery characteristics of the SOFC.
  • the present invention aims to provide a fuel electrode doubling as a support of a solid oxide fuel cell, whose conductivity and strength hardly lower through repetitive exposure to the reducing atmosphere/oxidazing atmosphere, as well as a method of producing such a fuel electrode.
  • the present invention also aims to provide a fuel-electrode-supported solid oxide fuel cell having a long life with improved cycle resistance of the fuel electrode, and also to provide a method of producing such a fuel-electrode-supported solid oxide fuel cell.
  • a fuel electrode doubling as a support of a solid oxide fuel cell includes: a three-dimensional network structure formed of oxide coarse particles with an average particle diameter of 30 to 90 ⁇ m and a first sol containing first oxide fine particles with an average particle diameter of 0.1 ⁇ m or smaller dispersed therein, where the oxide coarse particles are connected to one another via an aggregate of the first oxide fine particles; electrode particles having a function as an electrode catalyst dispersed in gaps of the three-dimensional network structure; and an aggregate of second oxide fine particles that is formed of a second sol containing the second oxide fine particles with an average particle diameter of 0.1 ⁇ m or smaller dispersed therein and connects the electrode particles to a surface in the gap of the three-dimensional network structure, wherein the oxide coarse particles are connected to one another without the electrode particle.
  • the aggregate of the second oxide fine particles connects the electrode particles to the surface in the gap of the three-dimensional network structure and, simultaneously, partially covers surfaces of the electrode particles.
  • the fuel electrode of the present invention further includes oxide particles with an average particle diameter of 0.2 to 1.0 ⁇ m that are dispersed in the gap of the three-dimensional network structure and partially cover the surfaces of the electrode particles. More preferably, the oxide particles are stabilized zirconia.
  • the electrode particles have an average particle diameter of 0.4 to 4.0 ⁇ m.
  • each of the oxide coarse particle, the first oxide fine particle and the second oxide fine particle is preferably at least one selected from a group including zirconia, alumina, silica and ceria, and is more preferably stabilized zirconia.
  • a fuel-electrode-supported solid oxide fuel cell according to the present invention includes the fuel electrode described above, a solid oxide electrolyte film formed on the fuel electrode, and an air electrode formed on the solid oxide electrolyte film.
  • a method of producing a fuel electrode doubling as a support of a solid oxide fuel cell according to the present invention includes: a first step of obtaining a compact from a mixture of powder of oxide coarse particles with an average particle diameter of 30 to 90 ⁇ m and a first sol containing first oxide fine particles with an average particle diameter of 0.1 ⁇ m or smaller dispersed therein; a second step of impregnating the compact with slurry prepared by mixing powder of electrode particles having a function as an electrode catalyst and a second sol containing second oxide fine particles with an average particle diameter of 0.1 ⁇ m or smaller dispersed therein; and a third step of, after the second step, obtaining a fuel electrode by calcining the compact.
  • the compact is preferably subjected to a heat treatment at temperature below a sintering temperature of the compact.
  • the slurry is prepared by further mixing powder of oxide particles with an average particle diameter of 0.2 to 1.0 ⁇ m. More preferably, the oxide particles are stabilized zirconia.
  • the powder of electrode particles has an average particle diameter of 0.4 to 4.0 ⁇ m.
  • total mass of solids in the first sol of the mixture and in the second sol of the slurry is 5 to 60 mass% of total mass of the mixture and the slurry.
  • each of the oxide coarse particle, the first oxide fine particle and the second oxide fine particle is preferably at least one selected from a group including zirconia, alumina, silica and ceria, and is more preferably stabilized zirconia.
  • a method of producing a fuel-electrode-supported sold oxide fuel cell according to the present invention includes, in addition to the steps of the method of producing the fuel electrode described above, a step of forming a solid oxide electrolyte film on the fuel electrode and a step of forming an air electrode on the solid oxide electrolyte film.
  • the solid oxide electrolyte film is preferably formed by, after the second step and before the third step, applying electrolyte material on the compact and, at the third step, calcining the electrolyte material together with the compact.
  • the fuel electrode doubling as the support of the solid oxide fuel cell of the present invention conductivity and strength hardly lower through repetitive exposure to the reducing atmosphere/oxidazing atmosphere.
  • a fuel electrode whose conductivity and strength hardly lower through repetitive exposure to the reducing atmosphere/oxidazing atmosphere may be produced.
  • the solid oxide fuel cell according to the present invention may achieve a long life with improved cycle resistance of the fuel electrode.
  • a solid oxide fuel cell having a long life with improved cycle resistance of the fuel electrode may be produced.
  • a method of producing a fuel electrode according to one embodiment of the present invention will be described with reference to FIG. 4 .
  • a mixture is obtained by mixing powder of yttria stabilized zirconia (YSZ) coarse particles as oxide fine particles and zirconia sol as first sol containing zirconia fine particles as first oxide fine particles dispersed therein.
  • the powder of YSZ coarse particles has an average particle diameter of 30 to 90 ⁇ m
  • the zirconia fine particles in the zirconia sol have an average particle diameter of 0.1 ⁇ m or smaller.
  • a compact with a thickness of approximately 0.2 to 3 mm is prepared from the mixture by carrying out, for example, a wet method.
  • the compact forms a three-dimensional network structure serving as a framework of the fuel electrode.
  • the compact is subjected to a heat treatment at temperature about, for example, 300 to 600 °C, which is lower than a sintering temperature of the compact.
  • slurry is prepared by mixing powder of NiO particles as electrode particles having a function as an electrode catalyst, zirconia sol as second sol containing zirconia fine particles as second oxide fine particles dispersed therein, and powder of YSZ particles as oxide particles.
  • the powder of NiO particles may have an average particle diameter of 0.4 to 4.0 ⁇ m
  • the zirconia fine particles in the zirconia sol have an average particle diameter of 0.1 ⁇ m or smaller.
  • the powder of YSZ particles has an average particle diameter of 0.2 to 1.0 ⁇ m. This slurry is used for filling gaps of the three-dimensional network structure with the NiO particles serving as the electrode particles.
  • the electrode particles in the present embodiment are NiO at a stage of production process of the fuel electrode, the electrode particles become Ni in principle at a stage of power generation by the SOFC.
  • expansion due to an irreversible oxidation reaction ofNi to become NiO in the course of use of the SOFC has been a problem to be solved.
  • step S5 the compact is impregnated with the slurry.
  • step S6 lastly, the compact is calcined, thus the fuel electrode is obtained.
  • the compact obtained at step S2 is the three-dimensional network structure 10 schematically illustrated in FIG. 1 .
  • the three-dimensional network structure 10 is formed of the YSZ coarse particles 12 connected to one another via a zirconia fine particle aggregate 14 originating in the zirconia sol.
  • the YSZ coarse particles 12 are very large as described above, the three-dimensional network structure 10 has numerous gaps formed therein.
  • nano-level zirconia fine particles form an aggregate that serves as a binder for firmly connecting the large YSZ coarse particles 12 to one another.
  • the compact is impregnated with the slurry and calcined to obtain a fuel electrode 30, as schematically illustrated in FIG. 2 .
  • the NiO particles 20 serving as the electrode particles are dispersed in the gaps 16 of the three-dimensional network structure. Since the production method, after forming the three-dimensional network structure 10, fills the gaps 16 with the NiO particles 20, the YSZ coarse particles 12 are connected to one another without the NiO particle 20. Further, a zirconia fine particle aggregate 22 generated from the zirconia sol as the second sol connects the NiO particles 20 to a surface in the gap 16 of the three-dimensional network structure.
  • an aggregate of the zirconia fine particles generated from the zirconia sol as the second sol may also form zirconia 24 that partially covers surfaces of the NiO particles 20.
  • Some of the YSZ particles originating in the powder of YSZ particles with the average particle diameter of 0.2 to 1.0 ⁇ m are connected to the surfaces of the NiO particles by the aggregate described above to form the zirconia 24 that partially covers the surfaces of the NiO particles 20, and the remaining YSZ particles are dispersed in the gap 16 (not illustrated).
  • a thickness of the fuel electrode 30 is not particularly limited, as long as being usable as the support of the SOFC, but is preferably 0.2 to 5 mm. This is because, when the thickness is 0.2 mm or more, the fuel electrode may be reliably used as the support and, when the thickness is 5 mm or less, a fuel gas may be supplied in proper quantities to an electrolyte surface.
  • a conventional nickel-zirconia cermet is formed by mixing NiO with an average particle diameter of approximately 1 ⁇ m and zirconia fine particles with an average particle diameter of approximately 0.5 ⁇ m, and thus does not have a strong framework structure and binding between zirconia fine particles/NiO is not strong, either. Therefore, when the fuel electrode is exposed alternately to a reducing atmosphere/oxidazing atmosphere in a repetitive manner, Ni is oxidized to NiO and a volume of the electrode particles irreversibly expands in the oxidazing atmosphere, deteriorating the strength of the fuel electrode as described above and generating cracks, and aggregation of the electrode particles is also progressed in the reducing atmosphere, lowering conductivity.
  • Such a problem applies also to the fuel electrode produced from fuel electrode material in PLT 2 which describes that YSZ coarse particles form a framework of the fuel electrode. Since the fuel electrode is produced from the fuel electrode material containing all of the YSZ coarse particles, the NiO particles and the YSZ fine particles, intervention by NiO particles between the YSZ coarse particles may not be avoided. Therefore, expansion due to change of the electrode particles from Ni to NiO directly affects the strength of the framework of the YSZ coarse particles. That is, this fuel electrode is not sufficiently strong, either, and has been causing generation of cracks due to deterioration of the strength thereof and also causing deterioration of the conductivity due to a progression of aggregation of the electrode particles.
  • a compact (three-dimensional network structure 10) serving as the framework of the fuel electrode is prepared in advance from a mixture containing no NiO particles and then the compact is filled with NiO particles 20 having the function as the electrode catalyst. Therefore, the YSZ coarse particles 12 of the three-dimensional network structure 10 forming the framework of the fuel electrode are connected to one another without the NiO particles 20 therebetween. Accordingly, since expansion due to the change of the electrode particle from Ni to NiO occurs only within the gap 16 of the three-dimensional network structure, the strength of the three-dimensional network structure 10 is not directly affected.
  • the zirconia sol is added to the mixture for preparing the compact and the slurry for filling NiO particles.
  • the zirconia sol in the mixture by a sol-gel reaction in the course of formation of the compact, forms the zirconia fine particle aggregate 14. Since the zirconia fine particle aggregate 14 serves as the binder for firmly connecting the YSZ coarse particles 12 to one another, the three-dimensional network structure 10 of the present embodiment has very high strength.
  • the zirconia sol in the slurry is introduced into the compact and, by the sol-gel reaction again in the course of the heat treatment for calcination, forms a zirconia fine particle aggregate.
  • this aggregate serves as the binder for firmly connecting the NiO particles 20 to the surface in the gap 16 of the three-dimensional network structure, aggregation of the electrode particles in the reducing atmosphere thereafter may be inhibited. Also, the aggregate also serves as partially covering the surfaces of the NiO particles 20, limiting an oxidation area of the Ni particles in power generation by the SOFC thereafter, and thus inhibiting irreversible expansion of the electrode particles.
  • the fuel electrode doubling as the support of the solid oxide fuel cell whose conductivity and strength hardly lower through repetitive exposure to the reducing atmosphere/oxidazing atmosphere may be obtained.
  • PLT 1 after forming a porous body having ceramic particles as a framework, electrode metal is introduced into holes of the porous body.
  • firm connection is not made because the aggregate of the zirconia fine particles formed by the sol-gel reaction is not used.
  • PLT 1 relates to an electrolyte-supported SOFC and thus may have a thin fuel electrode, this document has no consideration about deterioration of the strength of the fuel electrode.
  • this fuel electrode is applied to the fuel-electrode-supported SOFC, however, a problem of deterioration of the strength shall become obvious.
  • zirconia Although at least one selected from a group including zirconia, alumina, silica, and ceria may be used as the powder of oxide coarse particles, zirconia or ceria is preferable, and stabilized zirconia is particularly preferable. This is because an ionic transport number may be maintained in a stable manner in the reducing atmosphere/oxidazing atmosphere to which the fuel electrode is exposed.
  • the stabilized zirconia for example, yttria-stabilized zirconia (YSZ), calcia stabilized zirconia, and magnesia stabilized zirconia may be mentioned.
  • the average particle diameter of the powder of oxide coarse particles is 30 to 90 ⁇ m. This is because, when the average particle diameter is smaller than 30 ⁇ m, the gap of the three-dimensional network structure is too small to allow the Ni particles to form an appropriate conduction path and, when the average particle diameter exceeds 90 ⁇ m, the oxide coarse particles are calcined insufficiently and the strength of the fuel electrode is deteriorated.
  • the first oxide fine particles dispersed in the first sol As a material of the first oxide fine particles dispersed in the first sol, at least one selected from the group including zirconia such as stabilized zirconia, alumina, silica, and ceria may be used, too.
  • Concentration of solids of the first oxide fine particles in the first sol may be 10 to 60 mass%. This is because, when the concentration is under 10 mass%, an effect as the binder is lowered and, when the concentration is over 60 mass%, the Ni particles are covered and the sol has high viscosity and is cumbersome.
  • the average particle diameter of the first oxide fine particles is 0.1 ⁇ m or smaller. This is because, when the average particle diameter is over 0.1 ⁇ m, an effect to promote calcination of the oxide coarse particles is lowered.
  • any commercially available products may be used as the sol like that, and ZR-30BS produced by Nissan Chemical Industries, Ltd. may be used as zirconia sol, Almina sol-100 produced by Nissan Chemical Industries, Ltd. may be used as almina sol, Snowtex produced by Nissan Chemical Industries, Ltd. may be used as silica sol, and CZ-30B produced by Nissan Chemical Industries, Ltd. may be used as ceria sol.
  • the powder of oxide coarse particles is preferably 60 to 95 mass% of total solids in the mixture, and the solids in the first sol is preferably 5 to 40 mass% of total solids in the mixture.
  • Surfactants, dispersing agents, and thickeners for adjusting the viscosity may be added to the mixture, within a range not impairing the effects of the present invention.
  • the compact may be finished in a desired shape by a method of casting the mixture in a predetermined mold, a method of extrusion molding by adjusting the viscosity, or a method of impregnating, with the mixture, a sponge made of polyurethane or PVA having a network structure for transferring a framework structure.
  • the heat treatment is carried out in the atmosphere at temperature about, for example, 300 to 600 °C, which is below the sintering temperature of the compact, for about 1 to 5 hours. Carrying out the heat treatment at such a low temperature may reliably cause the sol-gel reaction of the zirconia sol and connect the YSZ coarse particles 12 via the zirconia fine particle aggregate 14. Thereby, the compact having high handling properties may be obtained. Since the temperature is set to 300 °C or higher, when an organic constituent is added to the mixture, the organic constituent may be burned down unfailingly.
  • a reason to set the temperature of the heat treatment as described above is as follows. That is, when the compact is sintered at its sintering temperature or higher in the heat treatment, the compact contracts greatly.
  • the compact does not contract any more, while the electrolyte material greatly contracts. Due to a contraction difference between the compact and the electrolyte material at this time, cracks may be generated in a solid oxide electrolyte film. Therefore, the present embodiment does not carry out sintering of the compact at this stage but connects the YSZ coarse particles 12 by a progress of the sol-gel reaction. Accordingly, a contraction amount at this stage is decreased and the contraction difference at the following step is reduced, thereby suppressing the generation of cracks.
  • NiO particles may be mentioned as the electrode particles, NiO particles to which copper or cobalt is added may also be used.
  • An average particle diameter of the electrode particles is preferably 0.4 to 4.0 ⁇ m. When the average particle diameter is 0.4 ⁇ m or larger, durability of the fuel electrode may be enhanced by sufficiently inhibiting aggregation of the electrode particles. When the average particle diameter is 4.0 ⁇ m or smaller, active sites of the electrode particles may be sufficiently secured and high electrode performances may be obtained.
  • the second sol may be similar to the first sol.
  • material of the oxide fine particles of the first sol may be either the same as, or different from, material of the oxide fine particles of the second sol.
  • the slurry includes, as the powder of oxide particles, powder of YSZ particles with the average particle diameter of 0.2 to 1.0 ⁇ m. Since some of the YSZ particles serve as the zirconia 24 for partially covering the surfaces of the NiO particles 20, the oxidation area of the Ni particle may be limited during power generation by the SOFC, and thereby the irreversible expansion of the electrode particles may be inhibited. Also, since the remaining YSZ particles are dispersed in the gap 16, aggregation of the Ni particles may be more inhibited.
  • the powder of oxide particles is not limited to YSZ but may be, similarly to the oxide coarse particles, at least one selected from the group including zirconia, alumina, silica, and ceria, and the stabilized zirconia is preferable.
  • the average particle diameter of the powder of oxide particles is 0.2 to 1.0 ⁇ m. This is because, when the average particle diameter is 0.2 ⁇ m or larger, the surfaces of the NiO particles 20 may be effectively covered and, when it is 1.0 ⁇ m or smaller, aggregation of the electrode particles in the reducing atmosphere may be sufficiently inhibited.
  • the powder of electrode particles is 40 to 80 mass%
  • solids of the second sol is 10 to 30 mass%
  • the powder of oxide particles is 10 to 30 mass%.
  • a kneading method of the slurry a planetary kneading machine, a planetary ball mill or a three-roller machine may be used.
  • surfactants, dispersing agents, and thickeners for adjusting the viscosity may be added to the slurry, within a range not impairing the effects of the present invention.
  • Step S5 is carried out by, for example, a method of immersing the compact obtained after step S3 in the slurry and keeping the compact in a desiccator under reduced pressure.
  • the reduced pressure is preferably around 10 mmHg, at which the slurry does not boil.
  • a decompression state is maintained in the desiccator for about five minutes and then atmospheric pressure is retrieved.
  • the ration of mass of the compact after step S3 relative to mass of electrode filled at step S5 is preferably 1:1-2.
  • mass of the total solids in the first sol of the mixture and in the second sol of the slurry is preferably 5 to 60 mass% of total mass of the mixture and the slurry. This is because, when the mass is less than 5 mass%, the progress of aggregation of the electrode particles may not be sufficiently suppressed and, when the mass is over 60 mass%, the formation of the conductive path by the Ni particles may be inhibited.
  • the calcining of the compact is carried out under conditions of, for example, at temperature of 1300 to 1500 °C in the atmosphere for 1 to 10 hours. Thereby, ceramic components in the compact and in the slurry are sintered and the fuel electrode is finalized.
  • the fuel electrode since the three-dimensional network structure having the framework formed of the oxide coarse particles is formed and the gaps of the three-dimensional network structure is filled with the electrode particles, the fuel electrode may be produced without using a pore-forming material such as carbon and the like.
  • the "average particle diameter” thereof means a particle diameter at a cumulative value 50% (50% cumulative particle diameter: D50) in a particle size distribution obtained by a laser diffraction scattering method.
  • the "average particle diameter” thereof means manufacturer's indications of commercially available products to be used.
  • "thicknesses of the fuel electrode, solid oxide electrolyte film and air electrode” are an average value of any five points in a polished cross-section of a sample filled with resin and observed by SEM.
  • the solid oxide fuel cell (SOFC) and a method of producing the same according to one embodiment of the present invention will be described.
  • a step of forming a solid oxide electrolyte film on the fuel electrode 30 and a step of forming an air electrode on the solid oxide electrolyte film are carried out.
  • This method enables obtainment of a fuel-electrode-supported SOFC 100 characterized in having the fuel electrode 30, a solid oxide electrolyte film 40 formed on the fuel electrode 30, and an air electrode 50 formed on the solid oxide electrolyte film 40 as illustrated in FIG. 3 .
  • the SOFC 100 has the fuel electrode 30 with improved cycle resistance and thus may achieve a long life.
  • the solid oxide electrolyte film and the air electrode may be produced by conventional methods. Typically, a ceramic material such as YSZ and the like is used as the electrolyte material and slurry thereof is applied on the fuel electrode 30, and then calcination is carried out.
  • a ceramic material such as YSZ and the like is used as the electrolyte material and slurry thereof is applied on the fuel electrode 30, and then calcination is carried out.
  • (La 0.8 Sr 0.2 ) MnO 3 may be used as a material of the air electrode and slurry thereof is applied on the calcined solid oxide electrolyte film, and then calcination is carried out. Since the present embodiment is for the fuel-electrode-supported SOFC, a thickness of the solid oxide electrolyte film 40 may be about 5 to 50 ⁇ m.
  • the compact and the electrolyte material are preferably calcined together. This process will be described with reference to FIG. 5 .
  • step S5 to impregnate the compact with the slurry the same steps of the embodiment illustrated in FIG 4 are carried out.
  • the electrolyte material is applied on the compact at step S7 and calcined together with the compact at step S8. Thereby, the fuel electrode 30 and the solid oxide electrolyte film 40 are completed simultaneously. As a result, the contraction difference between the compact and the electrolyte material may be reduced and generation of cracks may be suppressed.
  • the fuel electrode according to the present invention was produced.
  • powder of yttria-stabilized zirconia (YSZ) coarse particles (average particle diameter D50: 45 ⁇ m) and sol as the first sol containing zirconia fine particles dispersed therein (zirconia concentration: 30 mass%, average particle diameter: 63 nm, ZR-30BS produced by Nissan Chemical Industries, Ltd.) were mixed at a mass ratio of 79:21. From thus obtained mixture, a compact (thickness: 3 mm) was produced by the wet method. The compact was dried and subjected to a heat treatment at 500 °C in the atmosphere for 1 hour.
  • the powder of NiO particles (average particle diameter D50: 1.0 ⁇ m), the powder of YSZ particles (average particle diameter D50: 0.5 ⁇ m) and, as the second sol, the zirconia sol the same as the one described above were mixed such that the mass of their solids satisfy a ratio 4:1:1, and thereby slurry was prepared.
  • the compact after being subjected to the heat treatment was immersed in the slurry and held under reduced pressure at 10 mmHg in the desiccator for 5 minutes, followed by retrieval of the atmospheric pressure.
  • the compact thus obtained was calcined under conditions of 1400 °C in the atmosphere for 5 hours, and thereby a fuel electrode of Example 1 was produced.
  • a thickness of the fuel electrode measured by the aforementioned method was 2.5 mm.
  • This fuel electrode may serve as the support of the solid oxide fuel cell. Note that, in this example, mass of the total solids of the zirconia sol in the mixture and in the slurry (hereinafter, referred to as a "sol ratio") relative to the total mass of the mixture and the slurry is 15 mass%.
  • Example 2 In the same procedure as Example 1 other than changing a mixing ratio of the powder of YSZ coarse particles and the first sol so as to change the sol ratio to values shown in Table 1, fuel electrodes of Examples 2-4 (thickness: 2.5 mm) were produced.
  • Example 5 In the same procedure as Example 1 other than changing the average particle diameter D50 of the powder of YSZ coarse particles to values shown in Table 1, fuel electrodes of Example 5 and Comparative Examples 1-2 (thickness: 2.5 mm) were produced.
  • Example 6 In the same procedure as Example 1 other than using, as the first sol and the second sol, sol containing ceria fine particles dispersed therein (ceria concentration: 30 mass%, average particle diameter: 49 nm, CZ-30B produced by Nissan Chemical Industries, Ltd.) as shown in Table 1, a fuel electrode of Example 6 (thickness: 2.5 mm) was produced.
  • Example 7 In the same procedure as Example 1 other than using, instead of the YSZ coarse particles, powder of alumina coarse particles (average particle diameter D50: 45 ⁇ m) and, as the first sol and the second sol, sol containing hydrated alumina fine particles dispersed therein (specific gravity: 1.1, average particle diameter: 100 nm x 10 nm, alumina-sol-100 produced by Nissan Chemical Industries, Ltd.) and setting the sol ratio at 20 mass% as shown in Table 1, a fuel electrode of Example 7 (thickness: 2.5 mm) was produced.
  • alumina coarse particles average particle diameter D50: 45 ⁇ m
  • sol containing hydrated alumina fine particles dispersed therein specifically gravity: 1.1, average particle diameter: 100 nm x 10 nm, alumina-sol-100 produced by Nissan Chemical Industries, Ltd.
  • Example 8 In the same procedure as Example 1 other than using, instead of the NiO powder, NiO powder containing Cu added thereto such that the electrode particles are composed ofNi (70 mol%) and Cu (30 mol%), a fuel electrode of Example 8 (thickness: 2.5 mm) was produced.
  • Mixed powder was prepared from NiO powder (average particle diameter D50: 1.0 ⁇ m) of 45 mass%, YSZ powder (average particle diameter D50: 0.5 ⁇ m) of 45 mass%, and carbon as the pore-forming material (average particle diameter D50: 3 ⁇ m) of 1 mass%.
  • the mixed powder of 67 mass% is mixed to a solvent in which polyvinyl butyral of 5 mass% is dissolved in a terpineol, and thereby slurry was prepared.
  • slurry was molded into a sheet by a doctor blade method.
  • Thus obtained compact was calcined under conditions of temperature at 1400 °C in the atmosphere for 5 hours, and thereby a fuel electrode of Comparative Example 3 (thickness: 2.5 mm) was produced.
  • FIG. 6 and FIG. 7 are images of a scanning electron microscope (SEM) of the compact after being subjected to the heat treatment at 500 °C in Example 1. From those images, it can be seen that the aggregate of the zirconia fine particles in the zirconia sol intervenes between the YSZ coarse particles and thereby the YSZ coarse particles are connected to one another via the aggregate. This means that, even with the heat treatment at low temperature about 500 °C, by which the YSZ coarse particles alone cannot be connected to one another, the aggregate of the zirconia fine particles originating in the sol enables the YSZ coarse particles to connect to one another.
  • SEM scanning electron microscope
  • the YSZ coarse particles were connected to one another via the aggregate of the zirconia fine particles originating in the sol, thereby forming three-dimensional network structure. Similar structures were observed in the other examples. It is clear that, since the tree-dimensional network structure is formed and then impregnated with the slurry containing the NiO particles, the YSZ coarse particles are connected to one another without the NiO particles.
  • FIG. 8 is a referential SEM image of the compact of Example 1 after being subjected to the heat treatment not at 500 °C but at 800 °C. As can be seen from this image, aggregation and sintering of the zirconia fine particles in the zirconia sol have proceeded and the YSZ coarse particles are firmly connected to one another by the aggregate in which the zirconia fine particles are integrated with one another.
  • FIG. 9 is an image obtained by an energy dispersive X-ray (EDX) analysis of a cross-section of the fuel electrode of Example 1.
  • EDX energy dispersive X-ray
  • the green color represents distributions of Zr by the YSZ coarse particles and the zirconia fine particles originating in the sol
  • the red color represents a distribution of Ni of the NiO powder. From this image, it can be seen first that the NiO particles are dispersed in the gaps of the three-dimensional network structure. It can be also seen that, since the Ni in red are dotted and Zr in green are dispersed around the red dots in the gaps, the NiO particles are partially covered with the YSZ powder in the slurry and the aggregate of the zirconia fine particles originating in the sol. It is considered that, since the aggregate of the zirconia fine particles originating in the sol serves as the binder, the aggregate connects at least some of the NiO particles to the surface in the gap of the three-dimensional network structure. Similar images were observed in other examples
  • each fuel electrode was placed in a container maintained at 800 °C, in which a reducing atmosphere of H 2 at 99.9 % was maintained, for 30 minutes. Then, the atmosphere inside the container was replaced with nitrogen gas and the fuel electrode was held in the oxidizing atmosphere of the air for 30 minutes. This process was regarded as one cycle and repeated 50 times. Before and after the cycle test, to each of the fuel electrodes, conductivity was measured by a four-terminal method and three-point bending strength was also measured. Results are shown in Table 1.
  • the fuel electrode of Comparative Example 3 produced by the conventional method was damaged after the cycle test and thus measurement of conductivity and three-point bending strength thereof could not be conducted. It is considered that this is because, since this fuel electrode was produced from a mixture of the NiO powder and the YSZ powder, Ni was oxidized to NiO in the course of repetition of the reducing atmosphere/oxidizing atmosphere and strength of the fuel electrode was reduced due to irreversible swelling of the electrode particles, and also because the aggregation of the Ni particles has proceeded in the course of repetitions of those atmospheres.
  • Comparative Example 1 having the D50 of the powder of YSZ coarse particles smaller than a range thereof according to the present invention, the gaps of the three-dimensional network structure were so small that the conductive path could not be appropriately formed by the Ni particles and sufficient conductivity could not be obtained before and after the cycle. Also, in Comparative Example 2 having the D50 of the powder of YSZ coarse particles larger than the range thereof according to the present invention, since the sintering of the YSZ coarse particles did not sufficiently proceed, adequate three-point bending strength was not obtained both before and after the cycle.
  • the present invention is useful for an SOFC industry and various industries to which the SOFC is applied.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)
EP14150898.6A 2013-01-25 2014-01-13 Fuel electrode doubling as support of solid oxide fuel cell and method of producing same Not-in-force EP2760071B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2013012577A JP5562450B1 (ja) 2013-01-25 2013-01-25 固体酸化物型燃料電池の支持体を兼ねる燃料極およびその製造方法

Publications (2)

Publication Number Publication Date
EP2760071A1 EP2760071A1 (en) 2014-07-30
EP2760071B1 true EP2760071B1 (en) 2015-04-08

Family

ID=49920207

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14150898.6A Not-in-force EP2760071B1 (en) 2013-01-25 2014-01-13 Fuel electrode doubling as support of solid oxide fuel cell and method of producing same

Country Status (4)

Country Link
US (1) US20140212791A1 (ja)
EP (1) EP2760071B1 (ja)
JP (1) JP5562450B1 (ja)
KR (1) KR101572477B1 (ja)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7145844B2 (ja) * 2017-03-31 2022-10-03 大阪瓦斯株式会社 電気化学素子、電気化学モジュール、固体酸化物形燃料電池、および製造方法
JP2019086345A (ja) * 2017-11-03 2019-06-06 株式会社デンソー ガスセンサ用固体電解質、ガスセンサ
CN114094123A (zh) * 2021-11-17 2022-02-25 合肥国轩高科动力能源有限公司 阳极/电解质半电池、阳极支撑型固体氧化物燃料电池及其制法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3380681B2 (ja) 1996-06-27 2003-02-24 京セラ株式会社 固体電解質型燃料電池セルの製造方法
DE10031102C2 (de) * 2000-06-30 2003-03-06 Forschungszentrum Juelich Gmbh Verfahren zur Herstellung eines Verbundkörpers, insbesondere einer Elektrode mit temperaturbeständiger Leitfähigkeit
WO2004028966A1 (ja) * 2002-09-30 2004-04-08 Matsushita Electric Industrial Co., Ltd. 多孔体とその製造方法、およびその多孔体を用いた電気化学素子
JP2005203155A (ja) * 2004-01-14 2005-07-28 Sharp Corp 燃料電池の発電層、燃料電池セル及びその製造方法
EP1596458A1 (de) * 2004-03-29 2005-11-16 Sulzer Hexis AG Verfahren zur Entwicklung und Herstellung eines Anodenmaterials für eine Hochtemperatur-Brennstoffzelle
JP2006179412A (ja) * 2004-12-24 2006-07-06 Nissan Motor Co Ltd 燃料電池用電極触媒層、およびこれを用いた燃料電池
EP1870950B1 (en) * 2005-03-23 2011-08-17 Nippon Shokubai Co.,Ltd. Fuel electrode material for solid oxide fuel cell, fuel electrode using same, fuel-cell cell
JP5112623B2 (ja) * 2005-06-13 2013-01-09 学校法人長崎総合科学大学 燃料電池用電極の製造方法及び燃料電池
DE102006030393A1 (de) * 2006-07-01 2008-01-03 Forschungszentrum Jülich GmbH Keramische Werkstoffkombination für eine Anode für eine Hochtemperatur-Brennstoffzelle
JP5298469B2 (ja) * 2007-07-04 2013-09-25 日産自動車株式会社 燃料電池用ガス拡散電極
WO2009060752A1 (ja) * 2007-11-05 2009-05-14 Sumitomo Metal Mining Co., Ltd. 固体酸化物形燃料電池用の酸化ニッケル粉末材料とその製造方法、並びにそれを用いた燃料極材料、燃料極、及び固体酸化物形燃料電池
EP2371024B1 (en) * 2008-12-08 2018-11-21 Nextech Materials, Ltd Solid oxide fuel cell stack
JP2009224346A (ja) 2009-07-08 2009-10-01 Central Res Inst Of Electric Power Ind 固体電解質燃料電池用燃料極材料
EP2506353B1 (en) * 2009-11-24 2018-01-17 Mitsubishi Chemical Corporation Porous electrode base material, process for production thereof, precursor sheet, film-electrode assembly, and solid polymer fuel cell

Also Published As

Publication number Publication date
JP2014146421A (ja) 2014-08-14
KR20140095970A (ko) 2014-08-04
JP5562450B1 (ja) 2014-07-30
US20140212791A1 (en) 2014-07-31
EP2760071A1 (en) 2014-07-30
KR101572477B1 (ko) 2015-11-27

Similar Documents

Publication Publication Date Title
JP5489125B2 (ja) 全セラミックス固体酸化物形電池
JP5469795B2 (ja) サーメット電解質を用いたアノード支持固体酸化物燃料電池
JP6398647B2 (ja) 固体酸化物型燃料電池用アノードの製造方法および燃料電池用電解質層−電極接合体の製造方法
EP2254180A1 (en) Ceria and strontium titanate based electrodes
JP2007529852A5 (ja)
JP2008004422A (ja) 固体酸化物形燃料電池用電極及び固体酸化物形燃料電池並びにその製造方法
KR101637917B1 (ko) 수소이온 전도성 고체산화물 연료전지 및 이의 제조방법
JP6121954B2 (ja) 固体酸化物型燃料電池
KR20130123189A (ko) 고체산화물 연료전지용 음극 지지체 및 그 제조방법과 이를 포함한 고체산화물 연료전지
JP7021787B2 (ja) プロトン伝導性電解質
EP2760071B1 (en) Fuel electrode doubling as support of solid oxide fuel cell and method of producing same
JP4534188B2 (ja) 燃料電池用電極材料及びこれを用いた固体酸化物形燃料電池
EP2538474A2 (en) Material for solid oxide fuel cell, cathode including the material, and solid oxide fuel cell including the material
KR101662211B1 (ko) 연료극, 연료극 지지형 전해질막, 연료전지 및 연료극 지지형 전해질막의 제조방법
JP4018377B2 (ja) 固体電解質型燃料電池及びその製造方法
JP4462727B2 (ja) 固体電解質形燃料電池セル
KR20200019623A (ko) 고체 전해질 부재, 고체 산화물형 연료 전지, 수 전해 장치, 수소 펌프 및 고체 전해질 부재의 제조 방법
JP6664132B2 (ja) 多孔質構造体とその製造方法、及びそれを用いた電気化学セルとその製造方法
EP2884571A1 (en) Fuel electrode which also serves as supporting body of solid oxide fuel cell, and fuel electrode-supported solid oxide fuel cell
JP2009231052A (ja) 固体酸化物形燃料電池用セル及びその製造方法
JP5767743B2 (ja) 固体酸化物型燃料電池及び空気極材料
JP6088949B2 (ja) 燃料電池単セルおよびその製造方法
JP7135419B2 (ja) 多孔質焼結体
JP7086017B2 (ja) 水素極－固体電解質層複合体の製造方法、セル構造体の製造方法、及び、燃料電池の製造方法
JP5536271B1 (ja) 燃料極支持型の固体酸化物型燃料電池

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20140113

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: H01M 4/90 20060101ALI20141030BHEP

Ipc: H01M 8/12 20060101ALI20141030BHEP

Ipc: H01M 4/88 20060101ALI20141030BHEP

Ipc: H01M 4/86 20060101AFI20141030BHEP

INTG Intention to grant announced

Effective date: 20141118

RIN1 Information on inventor provided before grant (corrected)

Inventor name: OKAMOTO, TAKASHI

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 721154

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014000012

Country of ref document: DE

Effective date: 20150521

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 721154

Country of ref document: AT

Kind code of ref document: T

Effective date: 20150408

REG Reference to a national code

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20150408

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150708

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150810

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150808

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150709

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014000012

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150408

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

26N No opposition filed

Effective date: 20160111

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602014000012

Country of ref document: DE

Representative=s name: HERNANDEZ, YORCK, DIPL.-ING., DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160131

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602014000012

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160113

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160802

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170131

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20180113

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150408

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180113